Synthesis and crystal structure of 2,4-dihydro-4-[(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)imino]-5-methyl-2-phenyl-3H-pyrazol-3-one and its copper (II) complex

G. Cerchiaro, A. M. Da Costa Ferreira, A. B. Teixeira, H. M. Magalhaes, A. C. Cunha, V. F. Ferreira, L. S. Santos, M. N. Eberlin, Janet Mabel Scott Skakle, S. M. S. V. Wardell, J. L. Wardell

Research output: Contribution to journalArticle

19 Citations (Scopus)

Abstract

2-Diazo-3-methyl-1-phenyl-5-pyrazolone (2) and 2,4-dihydro-4-[(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)imino]-5-methyl-2-phenyl-3H-pyrazol-3-one (3) were obtained in a one-pot reaction from 3-methyl-1-phenylpyrazol-5-one (1), mesyl azide, and K2CO3 in MeOH or CH2Cl2 solution. NMR, IR and ESI mass spectra as well as the crystal structure are reported for red colored 3. The crystal structure determined at 150 K reveals that the corresponding bonds in the two phenylpyrazol-5-one moieties in each of the two independent "U" shaped molecules have essentially the same lengths, with an extensive delocalization in the central O-C-C-N-C-C-O fragment of the molecule. In particular, the hydrogen atom, formally a part of a hydroxyl group, is found near-midway [01-HY and 011-HY = 1.24(4) and 1.19(4) angstrom, in molecule 1, and O21-HX and O31-HY = 1.203(4) and 1.19(4) angstrom, in molecule 2] between the two oxygen atoms (formally in a carbonyl and a hydroxy group), with near linear O-H-O bond angles of 173.8(4)degrees and 172.7(4)degrees in the two independent molecules. All C-O bond lengths are in the narrow range of 1.27](3)-1.288(3) angstrom. Further, since this compound shows different coordinating groups, its binding ability towards copper(II) ions was investigated. A dark red complex 4, obtained by reaction of 3 with copper(II) ions at stoichiometric ratio, was characterized as a neutral 1: 1 species, [3:CuCl,], involving tautomeric forms, by ESI-MS, ESI-MS/MS, IR, UV/Vis and EPR spectra. Interestingly, copper coordination to ligand 3 occurs solely by oxygen atoms, in spite of the presence of nitrogen donor centers. The deprotonation of 4 was monitored by UV/Vis, and a corresponding pKa value was determined as (5.6 +/- 0.2). (c) 2006 Elsevier Ltd. All rights reserved.

Original languageEnglish
Pages (from-to)2055-2064
Number of pages9
JournalPolyhedron
Volume25
DOIs
Publication statusPublished - 2006

Keywords

  • pyrazole derivatives
  • copper complex
  • structural characterization
  • EPR and NMR spectroscopy
  • ESI mass spectrometry
  • BETA-DIKETONE INTERACTIONS
  • ENOL TAUTOMERS
  • HYDROGEN-BOND
  • SCHIFF BASE
  • CARBOHYDRATE OXIDATION
  • BIOLOGICAL EVALUATION
  • MOLECULAR-STRUCTURE
  • MAGNETIC-PROPERTIES
  • ORGANIC-SYNTHESIS
  • CU(II) COMPLEXES

Cite this

Cerchiaro, G., Da Costa Ferreira, A. M., Teixeira, A. B., Magalhaes, H. M., Cunha, A. C., Ferreira, V. F., ... Wardell, J. L. (2006). Synthesis and crystal structure of 2,4-dihydro-4-[(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)imino]-5-methyl-2-phenyl-3H-pyrazol-3-one and its copper (II) complex. Polyhedron, 25, 2055-2064. https://doi.org/10.1016/j.poly.2006.01.002

Synthesis and crystal structure of 2,4-dihydro-4-[(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)imino]-5-methyl-2-phenyl-3H-pyrazol-3-one and its copper (II) complex. / Cerchiaro, G.; Da Costa Ferreira, A. M.; Teixeira, A. B.; Magalhaes, H. M.; Cunha, A. C.; Ferreira, V. F.; Santos, L. S.; Eberlin, M. N.; Skakle, Janet Mabel Scott; Wardell, S. M. S. V.; Wardell, J. L.

In: Polyhedron, Vol. 25, 2006, p. 2055-2064.

Research output: Contribution to journalArticle

Cerchiaro, G, Da Costa Ferreira, AM, Teixeira, AB, Magalhaes, HM, Cunha, AC, Ferreira, VF, Santos, LS, Eberlin, MN, Skakle, JMS, Wardell, SMSV & Wardell, JL 2006, 'Synthesis and crystal structure of 2,4-dihydro-4-[(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)imino]-5-methyl-2-phenyl-3H-pyrazol-3-one and its copper (II) complex', Polyhedron, vol. 25, pp. 2055-2064. https://doi.org/10.1016/j.poly.2006.01.002
Cerchiaro, G. ; Da Costa Ferreira, A. M. ; Teixeira, A. B. ; Magalhaes, H. M. ; Cunha, A. C. ; Ferreira, V. F. ; Santos, L. S. ; Eberlin, M. N. ; Skakle, Janet Mabel Scott ; Wardell, S. M. S. V. ; Wardell, J. L. / Synthesis and crystal structure of 2,4-dihydro-4-[(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)imino]-5-methyl-2-phenyl-3H-pyrazol-3-one and its copper (II) complex. In: Polyhedron. 2006 ; Vol. 25. pp. 2055-2064.
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title = "Synthesis and crystal structure of 2,4-dihydro-4-[(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)imino]-5-methyl-2-phenyl-3H-pyrazol-3-one and its copper (II) complex",
abstract = "2-Diazo-3-methyl-1-phenyl-5-pyrazolone (2) and 2,4-dihydro-4-[(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)imino]-5-methyl-2-phenyl-3H-pyrazol-3-one (3) were obtained in a one-pot reaction from 3-methyl-1-phenylpyrazol-5-one (1), mesyl azide, and K2CO3 in MeOH or CH2Cl2 solution. NMR, IR and ESI mass spectra as well as the crystal structure are reported for red colored 3. The crystal structure determined at 150 K reveals that the corresponding bonds in the two phenylpyrazol-5-one moieties in each of the two independent {"}U{"} shaped molecules have essentially the same lengths, with an extensive delocalization in the central O-C-C-N-C-C-O fragment of the molecule. In particular, the hydrogen atom, formally a part of a hydroxyl group, is found near-midway [01-HY and 011-HY = 1.24(4) and 1.19(4) angstrom, in molecule 1, and O21-HX and O31-HY = 1.203(4) and 1.19(4) angstrom, in molecule 2] between the two oxygen atoms (formally in a carbonyl and a hydroxy group), with near linear O-H-O bond angles of 173.8(4)degrees and 172.7(4)degrees in the two independent molecules. All C-O bond lengths are in the narrow range of 1.27](3)-1.288(3) angstrom. Further, since this compound shows different coordinating groups, its binding ability towards copper(II) ions was investigated. A dark red complex 4, obtained by reaction of 3 with copper(II) ions at stoichiometric ratio, was characterized as a neutral 1: 1 species, [3:CuCl,], involving tautomeric forms, by ESI-MS, ESI-MS/MS, IR, UV/Vis and EPR spectra. Interestingly, copper coordination to ligand 3 occurs solely by oxygen atoms, in spite of the presence of nitrogen donor centers. The deprotonation of 4 was monitored by UV/Vis, and a corresponding pKa value was determined as (5.6 +/- 0.2). (c) 2006 Elsevier Ltd. All rights reserved.",
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author = "G. Cerchiaro and {Da Costa Ferreira}, {A. M.} and Teixeira, {A. B.} and Magalhaes, {H. M.} and Cunha, {A. C.} and Ferreira, {V. F.} and Santos, {L. S.} and Eberlin, {M. N.} and Skakle, {Janet Mabel Scott} and Wardell, {S. M. S. V.} and Wardell, {J. L.}",
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TY - JOUR

T1 - Synthesis and crystal structure of 2,4-dihydro-4-[(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)imino]-5-methyl-2-phenyl-3H-pyrazol-3-one and its copper (II) complex

AU - Cerchiaro, G.

AU - Da Costa Ferreira, A. M.

AU - Teixeira, A. B.

AU - Magalhaes, H. M.

AU - Cunha, A. C.

AU - Ferreira, V. F.

AU - Santos, L. S.

AU - Eberlin, M. N.

AU - Skakle, Janet Mabel Scott

AU - Wardell, S. M. S. V.

AU - Wardell, J. L.

PY - 2006

Y1 - 2006

N2 - 2-Diazo-3-methyl-1-phenyl-5-pyrazolone (2) and 2,4-dihydro-4-[(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)imino]-5-methyl-2-phenyl-3H-pyrazol-3-one (3) were obtained in a one-pot reaction from 3-methyl-1-phenylpyrazol-5-one (1), mesyl azide, and K2CO3 in MeOH or CH2Cl2 solution. NMR, IR and ESI mass spectra as well as the crystal structure are reported for red colored 3. The crystal structure determined at 150 K reveals that the corresponding bonds in the two phenylpyrazol-5-one moieties in each of the two independent "U" shaped molecules have essentially the same lengths, with an extensive delocalization in the central O-C-C-N-C-C-O fragment of the molecule. In particular, the hydrogen atom, formally a part of a hydroxyl group, is found near-midway [01-HY and 011-HY = 1.24(4) and 1.19(4) angstrom, in molecule 1, and O21-HX and O31-HY = 1.203(4) and 1.19(4) angstrom, in molecule 2] between the two oxygen atoms (formally in a carbonyl and a hydroxy group), with near linear O-H-O bond angles of 173.8(4)degrees and 172.7(4)degrees in the two independent molecules. All C-O bond lengths are in the narrow range of 1.27](3)-1.288(3) angstrom. Further, since this compound shows different coordinating groups, its binding ability towards copper(II) ions was investigated. A dark red complex 4, obtained by reaction of 3 with copper(II) ions at stoichiometric ratio, was characterized as a neutral 1: 1 species, [3:CuCl,], involving tautomeric forms, by ESI-MS, ESI-MS/MS, IR, UV/Vis and EPR spectra. Interestingly, copper coordination to ligand 3 occurs solely by oxygen atoms, in spite of the presence of nitrogen donor centers. The deprotonation of 4 was monitored by UV/Vis, and a corresponding pKa value was determined as (5.6 +/- 0.2). (c) 2006 Elsevier Ltd. All rights reserved.

AB - 2-Diazo-3-methyl-1-phenyl-5-pyrazolone (2) and 2,4-dihydro-4-[(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)imino]-5-methyl-2-phenyl-3H-pyrazol-3-one (3) were obtained in a one-pot reaction from 3-methyl-1-phenylpyrazol-5-one (1), mesyl azide, and K2CO3 in MeOH or CH2Cl2 solution. NMR, IR and ESI mass spectra as well as the crystal structure are reported for red colored 3. The crystal structure determined at 150 K reveals that the corresponding bonds in the two phenylpyrazol-5-one moieties in each of the two independent "U" shaped molecules have essentially the same lengths, with an extensive delocalization in the central O-C-C-N-C-C-O fragment of the molecule. In particular, the hydrogen atom, formally a part of a hydroxyl group, is found near-midway [01-HY and 011-HY = 1.24(4) and 1.19(4) angstrom, in molecule 1, and O21-HX and O31-HY = 1.203(4) and 1.19(4) angstrom, in molecule 2] between the two oxygen atoms (formally in a carbonyl and a hydroxy group), with near linear O-H-O bond angles of 173.8(4)degrees and 172.7(4)degrees in the two independent molecules. All C-O bond lengths are in the narrow range of 1.27](3)-1.288(3) angstrom. Further, since this compound shows different coordinating groups, its binding ability towards copper(II) ions was investigated. A dark red complex 4, obtained by reaction of 3 with copper(II) ions at stoichiometric ratio, was characterized as a neutral 1: 1 species, [3:CuCl,], involving tautomeric forms, by ESI-MS, ESI-MS/MS, IR, UV/Vis and EPR spectra. Interestingly, copper coordination to ligand 3 occurs solely by oxygen atoms, in spite of the presence of nitrogen donor centers. The deprotonation of 4 was monitored by UV/Vis, and a corresponding pKa value was determined as (5.6 +/- 0.2). (c) 2006 Elsevier Ltd. All rights reserved.

KW - pyrazole derivatives

KW - copper complex

KW - structural characterization

KW - EPR and NMR spectroscopy

KW - ESI mass spectrometry

KW - BETA-DIKETONE INTERACTIONS

KW - ENOL TAUTOMERS

KW - HYDROGEN-BOND

KW - SCHIFF BASE

KW - CARBOHYDRATE OXIDATION

KW - BIOLOGICAL EVALUATION

KW - MOLECULAR-STRUCTURE

KW - MAGNETIC-PROPERTIES

KW - ORGANIC-SYNTHESIS

KW - CU(II) COMPLEXES

U2 - 10.1016/j.poly.2006.01.002

DO - 10.1016/j.poly.2006.01.002

M3 - Article

VL - 25

SP - 2055

EP - 2064

JO - Polyhedron

JF - Polyhedron

SN - 0277-5387

ER -